RU2016107931A

RU2016107931A - Cyanized naphthalinbenzimidazole compounds

Info

Publication number: RU2016107931A
Application number: RU2016107931A
Authority: RU
Inventors: Мартин КЕНЕМАНН; Габриеле МАТТЕРН; Герхард Вагенбласт; Зорин ИВАНОВИЧИ; Роберт ЗЕНД
Original assignee: Басф Се
Priority date: 2013-08-05
Filing date: 2014-08-04
Publication date: 2017-09-11
Also published as: CN105452247B; RU2670218C2; EP3030628A1; US20160177177A1; JP2016534100A; JP6548648B2; WO2015019270A1; CN105452247A; KR20160038052A; TWI619712B; US9790423B2; EP3030628A4; BR112016002446A2; EP3030628B1; TW201512196A

Claims

1. Cyanated naphthalene benzimidazole derivatives of the formula I

,

or a mixture thereof

Where

R ^1, R ^2, R ^3, R ^4, R ^5, R ^6, R ^7, R ^8, R ⁹ and R ¹⁰ each independently represents hydrogen, cyano, or aryl which is unsubstituted or carry one or more identical or different substituents R ^Ar ,

Where

each R ^{Ar is} independently selected from the group consisting of cyano, hydroxyl, mercapto, halogen, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ alkylthio, nitro, -NR ^Ar2 R ^Ar3 , -NR ^Ar2 COR ^Ar3 , ^-CONR ^Ar2 R ^Ar3 , -SO ₂ NR ^Ar2 R ^Ar3 , -COOR ^Ar2 , -SO ₃ R ^Ar2 ,

C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, C ₂ -C ₃₀ alkynyl, where the last three radicals are unsubstituted or carry one or more R ^a groups,

C ₃ -C ₈ cycloalkyl, 3-8 membered heterocyclyl, where the last two radicals are unsubstituted or carry one or more R ^b groups, aryl, U-aryl, heteroaryl and U-heteroaryl, where the last four radicals are unsubstituted or carry one or more groups R ^b ,

Where

each R ^{a is} independently selected from cyano, hydroxyl, oxo, mercapto, halogen, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ alkylthio, nitro, -NR ^Ar2 R ^Ar3 , -NR ^Ar2 COR ^Ar3 , ^-CONR ^Ar2 R ^Ar3 , -SO ₂ NR ^Ar2 R ^Ar3 , -COOR ^Ar2 , -SO ₃ R ^Ar2 , C ₃ -C ₈ cycloalkyl, 3-8 membered heterocyclyl, aryl and heteroaryl, where cycloalkyl, heterocyclyl, aryl and heteroaryl radicals are unsubstituted or carry one or more R ^b groups;

each R ^{b is} independently selected from cyano, hydroxyl, oxo, mercapto, halogen, C ₁ -C ₂₀ alkoxy, C ₁ -C ₂₀ alkylthio, nitro, -NR ^Ar2 R ^Ar3 , -NR ^Ar2 COR ^Ar3 , ^-CONR ^Ar2 R ^Ar3 , -SO ₂ NR ^Ar2 R ^Ar3 , -COOR ^Ar2 , -SO ₃ R ^Ar2 , C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, C ₂ -C ₁₈ alkynyl, C ₃ -C ₈ - cycloalkyl, 3-8 membered heterocyclyl, aryl and heteroaryl, where the last four radicals are unsubstituted or carry one or more R ^bl groups,

each R ^{b1 is} independently selected from cyano, hydroxyl, mercapto, oxo, nitro, halogen, -NR ^Ar2 R ^Ar3 , -NR ^Ar2 COR ^Ar3 , ^-CONR ^Ar2 R ^Ar3 , -SO ₂ NR ^Ar2 R ^Ar3 , -COOR ^Ar2 , -SO ₃ R ^Ar2 , -SO ₃ R ^Ar2 , C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, C ₂ -C ₁₈ alkynyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkylthio,

U represents an —O—, —S—, —NR ^{Ar 1} -, —CO—, —SO— or —SO ₂ component;

R ^Arl , R ^Ar2 , R ^Ar3 each independently represents hydrogen, C ₁ -C ₁₈ -alkyl, 3-8-membered cycloalkyl, 3-8-membered heterocyclyl, aryl or heteroaryl, where the alkyl is unsubstituted or carries one or more groups R ^a where 3-8 membered cycloalkyl, 3-8 membered heterocyclyl, aryl and heteroaryl are unsubstituted or carry one or more R ^b groups;

provided that the compound of formula I contains at least one cyano group.

2. Cyanated naphthalene benzimidazole derivatives according to claim 1, wherein 0, 1, 2, 3, 4, 5, 6, or 7 of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents / represent aryl which is unsubstituted or has one or more identical or different R ^Ar substituents.

3. Cyanated naphthalene benzimidazole derivatives according to claim 1 or 2, wherein each R ^Ar independently represents cyano, C ₁ -C ₁₂ alkoxy, hydroxyl, halogen, nitro, -NR ^Ar2 R ^Ar3 , NR ^Ar2 COR ^Ar3 , ^-CONR ^Ar2 R ^Ar3 , -SO ₂ NR ^Ar2 R ^Ar3 , -COOR ^Ar2 , -SO ₃ R ^Ar2 , C ₁ -C ₁₈ -alkyl, which is an unsubstituted or mono- or polysubstituted hydroxyl, halogen, cyano, nitro or -NR ^Ar2 R group ^Ar3 , or C ₃ -C ₈ cycloalkyl or phenyl, where the last two radicals, in turn, are unsubstituted or mono- or polysubstituted with C ₁ -C ₁₈ alkyl, C ₁ -C ₁₂ alkoxy or cyano.

4. Cyanated naphthalene benzimidazole derivatives according to claim 1 or 2, in which at least one of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents phenyl, which is unsubstituted or has one or more identical or different substituents R ^Ar .

5. Cyanated naphthalene benzimidazole derivatives according to claim 4, in which at least one of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents phenyl which is unsubstituted or carries a cyano group.

6. Cyanated naphthalene benzimidazole derivatives according to claim 4, in which at least one of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents phenyl which is unsubstituted or carries 1, 2 or 3 substituents selected from C ₁ -C ₁₀ alkyl.

7. Cyanated naphthalene benzimidazole derivatives according to claim 1 or 2, in which one or two of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents / are cyano.

8. Cyanated naphthalene benzimidazole derivatives according to claim 1 or 2, in which one or two of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ represents / represent phenyl, 4-cyanophenyl or phenyl, which carries 1, 2 or 3 substituents selected from C ₁ -C ₁₀ alkyl, and the other R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ radicals are hydrogen; and zero, one or two of the radicals R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents / represent phenyl, 4-cyanophenyl or phenyl which carries 1, 2 or 3 substituents selected from C ₁ -C ₁₀ alkyl and other R ⁷ , R ⁸ , R ⁹ and R ¹⁰ radicals are hydrogen or cyano.

9. Cyanated naphthalene benzimidazole derivatives according to claim 1 or 2, in which one or two of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ represents / represent phenyl, 4-cyanophenyl, cyano or phenyl which bears 1, 2 or 3 substituents selected from C ₁ -C ₁₀ alkyl and the other R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ radicals are hydrogen; and zero, one, two or three of the radicals R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents / represent phenyl, 4-cyanophenyl or phenyl which carries 1, 2 or 3 substituents selected from C ₁ -C ₁₀ -alkyl, and other R ⁷ , R ⁸ , R ⁹ and R ¹⁰ radicals are hydrogen or cyano.

10. Cyanated naphthalene benzimidazole derivatives according to claim 1 or 2, which correspond to the formula I-A

,

or a mixture thereof

Where

R ³ and R ⁴ each independently represents cyano, phenyl, 4-cyanophenyl or phenyl which carries 1, 2 or 3 substituents selected from C ₁ -C ₁₀ alkyl; and

R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents hydrogen, cyano, phenyl, 4-cyanophenyl or phenyl, which carries 1, 2 or 3 substituents selected from C ₁ -C ₁₀ -alkyl.

11. Cyanated naphthalene benzimidazole derivatives according to claim 10, which correspond to the formula I-Aa

,

wherein

R ⁴ represents phenyl, 4-cyanophenyl or phenyl which carries 1, 2 or 3 substituents selected from C ₁ -C ₁₀ alkyl; and

two of the radicals R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents phenyl, 4-cyanophenyl or phenyl which carries 1, 2 or 3 substituents selected from C ₁ -C ₁₀ -alkyl, and other radicals R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are hydrogen.

12. Cyanated naphthalene benzimidazole derivatives according to claim 10, which correspond to a mixture corresponding to the formulas I-Ab and I-Ab '

,

in which

zero, one or two of the radicals R ⁷ , R ¹⁰ , R ⁸ and R ⁹ , if present, each independently represents phenyl, 4-cyanophenyl or phenyl which carries 1, 2 or 3 substituents selected from C ₁ -C ₁₀ -alkyl, and other radicals R ⁷ , R ¹⁰ , R ⁸ , R ⁹ , if present, are hydrogen.

13. Cyanated naphthalene benzimidazole derivatives of the formula I according to claim 1, in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the meanings as defined in . one,

obtained by the method in which

1.1) 1,8-naphthoic anhydride reacts with a diamine of formula (i)

,

wherein

each R * independently represents cyano or aryl, which is unsubstituted or has one or more identical or different R ^Ar substituents, where R ^{Arr is} defined above;

k is 0, 1 or 2,

to obtain the compounds of formula (ii)

,

1.2) the compound of formula (ii) obtained in stage 1.1) is subjected to bromination to obtain a compound of formula (iii)

,

wherein

n is 1 or 2;

m is 1 or 2, where the radicals (Br) _m are in one or more positions designated as *;

1.3) the compound of formula (iii) obtained in step 1.2) undergoes the substitution of bromine for aryl, which is unsubstituted or has one or more identical or different substituents R ^Ar , where R ^Ar has the meanings as defined in paragraph 1,

by reacting with an organometallic compound of formula iv,

,

wherein

Ar is aryl, which is mono - or polysubstituted R ^Ar ; and

Met represents B (OH) ₂ , B (OR ′) (OR ″), Zn-R ″ ″ or Sn (R *) ₃ ,

Where

R 'and R "' each independently represents hydrogen, C ₁ -C ₃₀ -alkyl, C ₅ -C ₈ -cycloalkyl, C ₆ -C ₁₄ -aryl or heteroaryl, or R 'and R" together represent C ₂ -C ₄ -alkylene, which optionally carries 1, 2, 3, 4, 5, 6, 7 or 8 substituents selected from C ₁ -C ₄ alkyl, C ₅ -C ₈ cycloalkyl, C ₆ -C ₁₄ - aryl and heteroaryl,

R ″ ″ represents C ₁ -C ₈ alkyl or phenyl, and

R * represents C ₁ -C ₈ alkyl or phenyl,

in the presence of a transition metal catalyst to give a compound of formula I

,

where 1 or 2 of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ represent aryl, which is unsubstituted or has one or more identical or different substituents R ^Ar , and other radicals R ¹ , R ² R ³ , R ⁴ , R ⁵ or R ⁶ are hydrogen, and

one or two of the radicals R ⁷ , R ⁸ , R ⁹ or R ¹⁰ represent aryl, which is unsubstituted or has one or more identical or different substituents R ^Ar , and the other radicals R ⁷ , R ⁸ , R ⁹ or R ¹⁰ represent represents hydrogen, cyano or aryl, which is unsubstituted or has one or more identical or different substituents R ^Ar ,

1.4) the compound (s) obtained in step 1.3) are optionally subjected to at least one separation and / or purification step;

or

2.1) 1,8-digalonaphthoic anhydride of the formula (v)

,

where Hal represents chlorine or bromine,

reacts with a diamine of formula (i)

,

Where

each R * independently represents cyano or aryl, which is unsubstituted or has one or more identical or different R ^Ar substituents, where R ^{Ar is} defined above;

k is 0, 1 or 2,

to obtain the compounds of formula (vi)

,

2.2) the compound of formula (vi) obtained in step 2.1) is subjected to bromination to obtain the compound of formula (vii)

,

wherein

n is 1 or 2;

2.3) the compound of formula (vii) obtained in step 2.2) undergoes a substitution reaction in which each Hal and each bromine atom is replaced by aryl, which is unsubstituted or has one or more identical or different substituents R ^Ar , where R ^Ar has the meanings as defined in paragraph 1,

or

the compounds of formula (vii) obtained in step 2.2) undergo a substitution reaction in which each Hal is replaced by aryl and some of the bromine atoms attached to the benzene ring of the benzimidazole moiety are replaced by aryl and other bromine atoms which are not replaced by aryl are substituted with hydrogen, where aryl is unsubstituted or has one or more identical or different substituents R ^Ar , where R ^Ar has the meanings as defined in paragraph 1,

by reaction with an organometallic compound of formula iv

,

in which Ar and Met have the meanings as defined above,

in the presence of a transition metal catalyst to give a compound of formula I

,

Where

R ³ and R ⁴ are aryl which is unsubstituted or has one or more identical or different R ^Ar substituents,

zero, one or two of the radicals R ⁷ , R ⁸ , R ⁹ or R ¹⁰ represent aryl, which is unsubstituted or has one or more identical or different substituents R ^Ar , and other radicals R ⁷ , R ⁸ , R ⁹ or R ¹⁰ are hydrogen, cyano or aryl, which is unsubstituted or has one or more identical or different R ^Ar substituents,

2.4) the compound (s) obtained in step 2.3) are optionally subjected to at least one separation and / or purification step;

or

3.1a) the compound of formula (vii) obtained in step 2.2), in which each Hal is chlorine, undergoes a substitution reaction where one of Hal is replaced by aryl and all or part of the bromine atoms attached to the benzene ring of the benzimidazole moiety are replaced on aryl, and other bromine atoms that are not substituted on aryl, are replaced by hydrogen, where aryl is unsubstituted or has one or more identical or different R ^Ar substituents, where R ^{Ar is} defined above,

by reaction with an organometallic compound of formula IV

,

in which Ar and Met have the meanings as defined above,

in the presence of a transition metal catalyst to give a compound of formula (viiia) and (viiib)

,

Where

R ³ , if present, is aryl which is unsubstituted or has one or more identical or different R ^Ar substituents;

R ⁴ , if present, is aryl which is unsubstituted or has one or more identical or different R ^Ar substituents;

zero, one or two of the radicals R ⁷ , R ⁸ , R ⁹ or R ¹⁰ represent aryl, which is unsubstituted or has one or more identical or different substituents R ^Ar , and other radicals R ⁷ , R ⁸ , R ⁹ or R ¹⁰ are hydrogen, cyano or aryl which is unsubstituted or has one or more identical or different R ^Ar substituents;

3.2a) if present, the compounds of formulas (viiia) and (viiib) undergo at least one purification and / or separation step;

3.3a) the compound (s) obtained in stage 3.1) or 3.2) is reacted with a metal cyanide to obtain a compound (s) of formula I,

and / or

,

Where

R ³ , if present, is aryl, which is an unsubstituted or mono- or polysubstituted R ^Ar group;

R ⁴ , if present, is aryl, which is an unsubstituted or mono- or polysubstituted R ^Ar group;

one or two of the radicals R ⁷ , R ⁸ , R ⁹ or R ¹⁰ represent aryl, which is unsubstituted or has one or more identical or different substituents R ^Ar , and the other radicals R ⁷ , R ⁸ , R ⁹ or R ¹⁰ represent represents hydrogen, cyano or aryl, which is unsubstituted or has one or more identical or different substituents R ^Ar ;

3.4a) the compound (s) obtained in step 3.3a) is optionally subjected to at least one separation and / or purification step;

or

3.1b1) a compound of formula (vi) obtained in step 2.1) is reacted with a metal cyanide to give a compound of formulas (ixa) and (ixb)

,

where (R *) _{k is} defined above;

3.1b2) compounds of formula (ixa) and (ixb) obtained in stage 3.1b1) are reacted with an organometallic compound of formula iv

,

where Ar and Met have the meanings as defined above,

in the presence of a transition metal catalyst to give a compound of formula I

,

Where

zero, one or two of the radicals R ⁷ , R ⁸ , R ⁹ or R ¹⁰ represent cyano or aryl, which is unsubstituted or has one or more identical or different substituents R ^Ar , and the remaining radicals R ⁷ , R ⁸ , R ⁹ or R ¹⁰ represents hydrogen;

3.1b3) the compound (s) of formula I optionally undergoes (are) at least one stage of separation and / or purification;

or

3.2b1) the compound of formula (vi) obtained in step 2.1) first reacts with the compound of formula (IV)

,

where Ar and Met have the meanings as defined above,

in the presence of a transition metal catalyst to give a compound of formula (ha) and (xb)

,

with metal cyanide to obtain compounds of the indicated formulas and then treated with metal cyanide;

3.2b2) the compounds of formulas (ha) and (xb) obtained in stage 3.2b1) react with metal cyanide to obtain a compound of the formulas

,

Where

3.2b3) the compound (s) obtained in step 3.2b2) optionally undergoes at least one separation and / or purification step;

or

4.1) the compounds of formula (vi) obtained in stage 2.1) are reacted with metal cyanide to give a compound of formula (I)

,

Where

4.2) the compound (s) of formula I, optionally undergoing at least one separation and / or purification step.

14. Cyanated naphthalene benzimidazole derivatives according to claim 13, which correspond to the compound of formula Ia or Ib

,

or a mixture of (Ia) and (Ib),

Where

Ar is aryl, which is optionally mono - or polysubstituted R ^Ar , where R ^Ar has the meanings as defined in paragraph 1;

n is 1 or 2, and

m is 1 or 2, and where (Ar) _m are in one of the positions indicated by *;

obtained by the method in which

a1) 1,8-naphthoic anhydride is reacted with 3,4-diaminobenzonitrile to give compounds of formulas IIa and IIb

,

A2) the compounds of formulas IIa and IIb obtained in stage a1) are subjected to bromination to obtain the compounds of formulas IIIa and IIIb

,

Where

n is 1 or 2,

m is 1 or 2 and where (Br) _m are in one of the positions indicated by *;

A3) compounds of formulas IIIa and IIIb obtained in stage a2) are reacted with an organometallic compound of formula IV,

,

where Ar and Met have the meanings as defined in paragraph 13;

in the presence of a transition metal catalyst to produce compounds of formulas Ia and Ib,

and

A4) the compounds of formulas Ia and Ib obtained in stage a3), optionally undergo at least one stage of separation and / or purification.

15. Cyanated naphthalene benzimidazole derivatives according to claim 13, which correspond to the compound of the formula Ic or Id

or a mixture of (Ic) and (Id),

Where

R ³ represents aryl, which is an unsubstituted or mono - or polysubstituted group of R ^Ar ;

R ⁴ represents aryl, which is an unsubstituted or mono - or polysubstituted group of R ^Ar ;

Ar is aryl, which is an unsubstituted or mono- or polysubstituted R ^Ar group;

R ^Ar has the meanings as defined in paragraph 1; and

n is 1 or 2,

obtained by the method in which

b1) 4,5-digalonaphthoic anhydride of the formula V

,

wherein

Hal is bromine or chlorine,

reacts with 3,4-diaminobenzonitrile to give compounds of formulas VIa and VIb

b2) the compounds of formulas VIa and VIb obtained in stage b1) are brominated to obtain the compounds of formulas VIIa and VIIb

,

wherein

n is 1 or 2,

b3) the compounds of formulas VIIa and VIIb obtained in stage b2) are reacted with an organometallic compound of the formula IV

,

where Ar and Met have the meanings as defined in clause 13

in the presence of a transition metal catalyst to give compounds of formulas Ic and Id,

b4) the compounds of formulas Ic and Id obtained in step b3) are optionally subjected to at least one separation and / or purification step.

16. Cyanated naphthalene benzimidazole derivatives according to claim 13, which correspond to the compound of the formula Ie or If

or mixtures of (Ie) and (If),

Where

each R * independently represents cyano or aryl, which is unsubstituted or has one or more identical or different R ^Ar substituents,

R ^Ar has the meanings as defined in paragraph 1; and

k is 0, 1 or 2;

obtained by the method in which

c1) 4,5-digalonaphthoic anhydride of the formula V

,

Where

Hal is bromine or chlorine,

reacts with a compound of formula VIII

,

where R * is defined above; and k is 0, 1 or 2,

to obtain the compounds of formula IX

c2) a compound of formula IX obtained in step c1) is reacted with an organometallic compound of formula IV

,

where Ar and Met have the meanings as defined in clause 13

in the presence of a transition metal catalyst to produce compound (s) of formulas Xa and / or Xb,

,

c3) if present, the compounds of formulas Xa and / or Xb obtained in step c2) are separated;

c4) the compound (s) of formulas Xa and / or Xb obtained in step c2) or c3) are reacted with a metal cyanide to give a compound of formulas Ie and / or If,

or

c2a) a compound of formula IX obtained in step c1) is reacted with a metal cyanide to obtain a compound (s) of formulas XIa and / or XIb

,

and

c3a) the compound (s) of formulas XIa and / or XIb obtained in step c2a) are reacted with an organometallic compound of formula IV

,

where Ar and Met have the meanings as defined in paragraph 13,

in the presence of a transition metal catalyst to produce compound (s) of the formula (s) Ie and / or If,

c5) the compound (s) of the formula (s) Ie and / or If obtained in step c3) or c3a) are optionally subjected to at least one separation and / or purification step.

17. Cyanated naphthalene benzimidazole derivatives according to claim 13, which correspond to the compound of formula Ig

,

wherein

each R * independently represents cyano or aryl, which is unsubstituted or has one or more identical or different substituents R ^Ar , where

R ^Ar has the meanings as defined in paragraph 1; and

k is 0, 1 or 2;

obtained by the method in which

d1) a compound of formula IX

,

wherein

R * is defined above, and

k is 0, 1, or 2,

reacts with metal cyanide to give a compound of formula Ig,

and

d2) the compounds of formula Ig obtained in step d1) are optionally subjected to at least one separation and / or purification step.

18. Cyanated naphthalene benzimidazole derivatives according to claim 13, which correspond to the compound Ih, Ii, Ik or Im

,

or mixtures (Ih) - (Im),

Where

Ar is aryl, which is an unsubstituted or mono- or polysubstituted group R ^Ar , and R ^Ar has the meanings as defined in paragraph 1; and

n * is 0, 1 or 2;

obtained by the method in which

e1) compounds of formulas VIIa and VIIb

,

Where

n is 1 or 2,

undergo a substitution reaction in which one Hal and each bromine atom is replaced by aryl, which is unsubstituted or has one or more identical or different R ^Ar substituents, where R ^Ar has the meanings as defined in paragraph 1,

or

the compounds of formulas (VIIa) and (VIIb) undergo a substitution reaction in which one Hal is replaced by aryl, and some of the bromine atoms attached to the benzene ring of the benzimidazole moiety are replaced by aryl, and other bromine atoms that are not replaced by aryl are replaced by hydrogen, where aryl is unsubstituted or has one or more identical or different substituents R ^Ar , where R ^Ar has the meanings as defined in paragraph 1,

by reaction with an organometallic compound of formula IV

,

Where

Ar and Met have the meanings as defined in clause 13,

in the presence of a transition metal catalyst to give compounds of formulas XIIa, XIIb, XIIc and XIId

,

Where

n * is 0, 1 or 2; and

Ar is as defined above;

f2) if present, the compounds of formulas (XIIa), (XIIb), (XIIc) and (XIId) are separated to obtain a mixture of compounds of formulas (XIIa) and (XIIb) and a mixture of compounds of formulas (XIIc) and (XIId);

e3) the compounds obtained in step e1) or e2) are reacted with metal cyanide to give compounds of formulas Ih, Ii, and / or Ik and Im;

e4) the compound (s) of the formula (formula) Ih, Ii and / or Ik or Im obtained in step e3) are optionally subjected to at least one separation and / or purification step.

19. A color converter containing at least one polymer as a matrix and at least one cyanated naphthalene benzimidazole compound of the formula I or a mixture of such compounds according to any one of claims. 1-18 as a fluorescent dye.

20. The color Converter according to claim 19, in which at least one cyanated naphthalene benzimidazole compound is selected from compounds of formulas (1) to (54) and mixtures thereof

21. The color converter according to claim 19 or 20, wherein the at least one polymer consists essentially of polystyrene, polycarbonate, polymethyl methacrylate, polyvinyl pyrrolidone, polymethacrylate, polyvinyl acetate, polyvinyl chloride, polybutene, silicone, polyacryl, epoxy resin, polyvinyl polyvinyl alcohol polyvinylidene chloride (PVDC), polystyrene acrylonitrile (SAN), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyvinyl butyrate (PVB), polyvinyl chloride (PVC), polyamides, polyoxymethylene, polyimides, polyether yes or mixtures thereof, in particular polycarbonate, polystyrene or polyethylene terephthalate.

22. The color converter according to claim 19 or 20, wherein the color converter further comprises at least one inorganic white pigment as a scattering body.

23. The color Converter according to claim 19 or 20, containing at least one additional organic fluorescent dye selected from compounds or mixtures of formulas XIV, XV and XVI

,

Where

p is from 1 to 4,

R ¹¹ , R ¹² each independently represents C ₁ -C ₃₀ -alkyl, C ₃ -C ₈ -cycloalkyl, aryl, hetaryl, aryl-C ₁ -C ₁₀ -alkylene, where the aromatic ring in the last three radicals is unsubstituted or mono - or polysubstituted C ₁ -C ₁₀ -alkyl,

R ¹³ is C ₁ -C ₃₀ alkoxy or aryloxy, which is an unsubstituted or mono- or polysubstituted group of C ₁ -C ₁₀ alkyl, where R ¹³ radicals are in one or more positions designated as *.

24. The color converter according to claim 23, wherein the additional organic fluorescent dye is selected from N, N'-bis (2,6-diisopropylphenyl) -1,6,7,12-tetraphenoxyperylene-3,4; 9,10-tetracarboxamide, N, N'-bis (2,6-diisopropylphenyl) -1,7-di (2,6-diisopropylphenoxy) perylene-3,4; 9,10-tetracarboxamide, N, N'-bis (2,6-diisopropylphenyl ) -1,6-di (2,6-diisopropylphenoxy) perylene-3,4; 9,10-tetracarboxamide, N, N'-bis (2,6-diisopropylphenyl) -1,7-di (p-tert- octylphenoxy) perylene-3,4; 9,10-tetracarboxamide, N, N'-bis (2,6-diisopropylphenyl) -1,6-di (p-tert-octylphenoxy) perylene-3,4; 9,10- tetracarboxamide, N, N'-bis (2,6-diisopr pilphenyl) -1,7-diphenoxyperylene-3,4; 9,10-tetracarboxamide, N, N'-bis (2,6-diisopropylphenyl) -1,6-diphenoxyperylene-3,4; 9,10-tetracarboxamide and their mixtures.

25. The color converter according to claim 19 or 20, comprising, as an additional fluorescent dye, at least one inorganic fluorescent dye selected from aluminates, silicates, nitrides and garnets doped with rare earth elements, especially doped with yttrium aluminum garnet.

26. The use of a color converter according to any one of paragraphs. 19-25 to convert the light created by the LED.

27. The use of the color converter according to claim 26 for converting light that was created by a blue diode.

28. The use of a color converter according to any one of paragraphs. 19-25 for the conversion of light created by acid.

29. A lighting device comprising at least one LED and at least one color converter according to any one of paragraphs. 19-25.

30. The lighting device according to claim 29, comprising at least one LED and at least one color converter according to any one of claims. 19-25, in which the LED and the color converter are in the design of the remote phosphor.

31. A device that produces electrical energy when illuminated, containing a photovoltaic cell and a color converter according to any one of paragraphs. 19-25, where at least a portion of the light not absorbed by the photovoltaic cell is absorbed by the color converter.